Binder for mineral wool products

ABSTRACT

Process for providing a binder for mineral wool products, said process comprising the steps of: mixing together under reactive conditions a carboxylic acid with an alkanolamine, whereby optionally these are firstly mixed to provide a resin, which resin is subsequently reacted with a separate carboxylic acid group containing polymer.

The invention relates to a process for providing a binder for mineral fibers, i.e. man made vitreous fibers, for example glass, slag or stone wool, a binder obtainable via such a process, and a mineral wool product comprising such a binder.

Mineral wool products generally comprise mineral fibers bonded together by a cured thermoset polymeric material. One or more streams of molten glass, slag or stone are drawn into fibers and blown into a forming chamber where they are deposited as a web on to a travelling conveyer. The fibers, while airborne in the forming chamber and while still hot are sprayed with a binder. The coated fibrous web is then transported from the chamber to a curing oven where heated air is blown through the mat to cure the binder and rigidly bond the mineral wool fibers together.

Phenol-formaldehyde binders are widely used in the mineral wool industry since they have a low viscosity in the uncured state, yet still form a rigid thermoset polymeric matrix for the mineral fibers when cured.

However the use of phenol formaldehyde binders is becoming increasingly undesirable due to the use and release of environmentally unfavourable chemicals during the process.

The use of β-hydroxyalkylamides to cure polycarboxy polymers such as polyacrylic acid in order to provide a binder is known.

A problem with polyacrylics cured by β-hydroxyalkylamides is that mineral wool products bound with such a resin normally exhibit good mechanical properties before ageing, but after exposure to high humidities and increased temperatures, for example above 40 degrees centigrade, the mechanical properties are drastically reduced.

There is therefore a desire to develop a binder which improves on the known binders.

An object of the present invention is to provide an alternative binder aimed at overcoming one or more of these problems.

According to a first aspect of the present invention, there is provided a process for providing a binder for mineral wool products said process comprising the steps of:

-   -   mixing together under reactive conditions a carboxylic acid with         an alkanolamine.

The resulting binder when utilized for a mineral wool product, provides the mineral wool product with desirable mechanical properties after ageing, subjection to tear strain and exposure to high humidities and increased temperatures.

The carboxylic acid and the alkanolamine are preferably firstly mixed together under reactive conditions to provide a resin, which resin optionally is subsequently mixed with a separate carboxylic acid group containing polymer to form a binder.

The carboxylic acid is preferably a di-, tri-, or tetra carboxylic acid having a molecular weight of about 1000 or less, preferably about 500 or less, and most preferably about 200 or less, most preferably a di-carboxylic acid having the general formula: COOH—(CR₁R₂)_(n)—COOH wherein n≧2 and preferably n≧4, and wherein R₁ and R₂ are independently selected from H or a lower alkyl group, preferably a methyl or ethyl group.

The carboxylic acid is preferably selected from the group consisting essentially of: adipic acid, citric acid, trimellitid acid, sebacic acid, azelaic acid, and. succinic acid and is most preferably adipic acid.

The alkanolamine is preferably selected from the group comprising di, and tri-alkanolamines, and can be a secondary beta-hydroxy alkylamine, preferably an N-substituted alkanolamine selected from the group consisting essentially of, di-ethanolamine, 1-(m)ethyldiethanolamine, n-butyldiethanolamine, 3-amino-1,2-propanediol, 2-amino-1,3,-propanediol, tris(hydroxymethyl)aminomethane, most preferably being diethanolamine.

The mole ratio of the carboxylic acid to the alkanolamine in the binder preferably lies in the range of 0.1-1:1-0.1 and the weight percentage of the carboxylic acid group containing polymer in the binder can lie in the range of 0.5-50, for example 10-40, preferably 15-30, most preferably about 20.

The alkanolamine is preferably firstly heated to around 60° C., whereafter the carboxylic acid is added and the temperature of this mixture is subsequently raised to about at least 90° C., preferably a temperature lying in the range of about 95-200, for example about 120-150° C.

The carboxylic acid group containing polymer preferably has a molecular weight lying in the ranges of 1000-300000, for example 1000-250000, preferably 1000-200000 most preferably having a molecular weights of around 60000, around 100000 and around 190000.

The carboxylic acid group containing polymer preferably comprises one or more of the following: polyacrylic acid, polymethacrylic acid, polymaleic acid and/or co-polymers thereof, preferably being selected from one or more of the following:

-   -   HF-05A, Rohm & Haas,     -   Acusole 190, Rohm & Haas,     -   Acumer 1510, Rohm & Haas,     -   41.600-2, from the Aldrich Chemical Company Inc.

One or more of the following additives can be added to the binder:

-   -   a coupling agent, for example an aminosilane, preferably         gamma-aminopropyltriethoxysilane,     -   a polymerisation accelerator, ascuring accelerator and         optionally further standard mineral wool binder additives.

In order to improve the water solubility of the resin a base might be added till a pH up to 7. The base is preferably mixed with a polyacrylic acid and added to the resin reaction mixture after the resin reaction is preferably stopped by water addition. Accordingly, the base can first be added after the resin is prepared. Suitable bases include NH₃, DEA, TEA.

Further characteristics are referred to in claims 18-23.

In order to improve the ageing constancy properties a silane may be added. The silane usually but is not restricted to be added during the binder preparation or directly (separately) at the line. The amount would normally be in the range from 0.1% to 5% (0.2%-3%). Preferred amount is approximately 1%.

According to further aspects of the present invention there is provided a binder obtainable according to this process, a process for providing a mineral wool product, a mineral wool product and the use of a reaction mixture of an alkanolamine and a carboxylic acid, optionally mixed with a carboxylic acid group containing polymer, as a binder for a mineral wool product.

The invention will now be further illustrated by way of the following examples and results.

EXAMPLE 1

158 g diethanolamine was placed in a 1-liter glass reactor provided with a double jacket and an agitator. Temperature of the diethanolamine was raised to 60° C. whereafter 99 g adipic acid was added slowly. The temperature was raised to 95° C. After a reaction time of 1 hour at about 95° C. the reaction was stopped by the addition of 200 g water. The reaction product was a clear, colourless, low viscous liquid, dilutable with water.

EXAMPLE 2

158 g diethanolamine was placed in a 1-liter glass reactor provided with a double jacket and an agitator. Temperature of the diethanolamine was raised to 60° C. whereafter 175 g adipic acid was added slowly. The temperature was raised to 95° C. After a reaction time of 1 hour at about 95° C. the reaction was stopped by the addition of 200 g water. The reaction product was a clear, colourless, low viscous liquid, dilutable with water.

EXAMPLE 3

67.2 g triethanolamine was mixed with 33.0 g adipic acid at room temperature. After the solution had turned clear 60 ml temperate water was added. The mixture was a clear, colourless, low viscous liquid, dilutable in water.

EXAMPLE 4-6

Resins were made using the same procedure as in example 1. The following amounts of chemicals were used: TABLE 1 Alkanolamine Polycarboxylic acid Water Example 4 158 g Diethanolamine 243 g Azelaic Acid 200 ml Example 5 158 g Diethanolamine 141 g Sebacic Acid 200 ml Example 6 158 g Diethanolamine  89 g Succinic Acid 200 ml

EXAMPLE 7

158 g diethanolamine was placed in a 1-liter glass reactor provided with a double jacket and an agitator. The temperature of the diethanolamine was raised to 60° C. whereafter 99 g adipic acid was slowly added. The temperature was subsequently raised to about 130° C., the temperature-being maintained between 128 and 135° C. After a reaction time of 3 hours the reaction was stopped by the addition of water.

All the produced reaction products in examples 4-7 were clear colourless low viscous liquids, dilutable in water.

EXAMPLE 8

Preparation and testing of selected binder samples to evaluate the binding strength towards shots with mineral fibre composition (Grit bar test). As shots are considered unfiberized fiber material with identical composition as the fibers.

Shots with size between 0.25 and 0.5 mm diameter were used to make bars with dimensions 140 mm×25 mm×10 mm.

A binder solution was prepared comprising 80% of the resins from examples 1-7 mixed at room temperature with 20% of a commercial polyacrylic resin.

As polyacrylic acids were used the commercial types from Rohm & Haas: HF-05A, Acusole 190 and Acumer 1510, and a polyacrylic acid with an average mole weight of 250.000 (Aldrich Chemical Company Inc. 41.600-2).

For making the bars 90 ml binder solution with 15% solids content and 0.2% silane coupling agent of binder solids were mixed with 450 g shots.

The coupling agent was gamma-aminopropyltriethoxysilane.

Out of the 450 g shots mixed with binder solution, 8 bars were made which were cured 2 hours at 200° C. in an incubator.

Four of the bars were broken directly (dry strength), the other 4 are placed 3 hours in 80° C. water before they are broken (wet strength).

The binding strength was determined by breaking the bars in a measuring device, where the clamping length is 100 mm and the velocity of the compressing beam was 10 mm/min. Using the clamping length, width and thickness of the bars, the bending strength was determined in N/mm².

For comparison a commercial product Primid XL-552 from EMS Chemie AG was used. Primid XL-552 is the reaction product of a dimethylester of adipic acid and diethanolamine, whereby the inventors have shown that 100% Primid is not curable since only free OH-groups are present which do not cross-link. A mixture of 80% primid and 20% PAA yielded a very fast curing time (45 s (HF-05) and 20s (Mw 250,000) at 200° C.) but the products have no remaining strength after ageing. The results are shown in table 2. TABLE 2 Remaining Unaged Aged strength Polyacrylic strength strength (aged/ Resin acid N/mm² N/mm² unaged) 80% 20% HF05 9.6 2.0 21% Example 1 80% 20% PAA 9.7 4.6 47% Example 1 MW 250000 80% 20% HF05 10.0 5.3 53% Example 2 80% 20% PAA 6.9 4.5 66% Example 2 MW 250000 80% 20% HF05 7.7 6.2 81% Example 3 comparison 20% HF05 3.6 0 0% example 80% Primid XL-552 60% 40% HF05 8.1 4.0 49% Example 2 20% 80% HF05 8.5 1.5 18% Example 2 20% 80% PAA, 4.5 4.0 89% Example 2 Mw 250,000 80% 20% PAA 6.6 3.1 47% Example 4 MW 2,000 80% 20% PAA 8.0 4.7 59% Example 5 Mw 2,000 80% 20% PAA 7.5 0.4 5% Example 6 Mw 250,000 80% 20% 8.0 2.4 30% Example 7 Acusol 190 80% 20% Acumer 9.2 3.2 35% Example 7 1510 Measurement of Curing times for Selected Examples

A few droplets of the binder to be examined were placed on a microscope cover glass. The glass was dried in a heating cupboard at 90° C. for 45 min.

After drying the cover glass was placed on a heating stage at 250° C. and while stirred with a piece of metal wire (straightened paper-clips) the time was measured until the binder was cured.

The results are shown in table 3. TABLE 3 Results Polyacrylic Curing time Curing time Resin acid 200° C. 250° C. 80% Example 1 20% HF05 — 90 s 80% Example 1 20% PAA, Mw — 25 s 250,000 80% Example 2 20% HF05 140-160 s 45 s 80% Example 2 20% PAA, Mw — 25 s 250,000 80% Example 4 20% HF05 173 s 43 s 80% Example 5 20% HF05 285 s 50 s 80% Example 7 20% 35 s — Acusol 190 80% Example 7 20% Acumer 30 s — 1510

As polyacrylic acids were used the commercial types from Rohm & Haas: HF-05A, Acusole 190 and Acumer1510, and two pure polyacrylic acids with average mole weights of 2000 and 250,000 respectively (Aldrich Chemical Company Inc. 32,366-7 and 41,600-2)

EXAMPLE 9

20.8 kg Diethanolamine were transferred to a 80 liter steel reactor provided with an agitator and a heating/cooling jacket and heated to 60° C. 23.0 kg Adipic Acid were added to the reactor in 5 portions and the temperature raised to a reaction temperature of 95° C. After reaction for 1 hour 26.3 kg temperate water were added, whereafter the resin was cooled to room temperature.

The resulting resin was a clear colourless low viscous liquid dilutable with water.

At room temperature 80% of the above resin was mixed with 20% of a commercial Polyacrylic resin from Rohm & Haas: HF-05.

The produced resin was after mixing with water and addition of 0.2% of a silane coupling agent used as a binder in a production trial on a standard stonewool line. The product produced was a standard slab with a density of 100 kg/m³, 100 mm thickness and with approximately 3% binder content.

As a comparison a trial was made with two commercial polyacrylic resins. HF-05 and QRXP 1513 both from Rohm & Haas. Both resins were diluted with water and added 0.2% of a silane coupling agent.

The coupling agent was γ-aminopropyltriethoxysilane.

The mechanical strengths were measured according to EN1607 (delamination strength). The delamination strength was measured on both unaged and after exposure to high humidity and increased temperature in a climate chamber (70° C./95 RH; aged samples) Results from the testing are shown in tables 4, 5 and 6 below. TABLE 4 Delamination Delamination strength strength Aged Binder Oil Density Unaged (70° C./95% Remaining Binder content content Kg/m³ kPa RH) kPa strength Binder 3.1% 0.2% 98 9.7 4.0 41% according Example 8 Comparison 3.3% 0.2% 101 7.2 1.3 18% example HF-05 Comparison 3.1% 0.2% 98 12.6 1.6 13% example QRXP Comparison 3.3% 0.2% 99 10.9 4.6 42% example Standard phenolic resin

EXAMPLE 10

TABLE 5 Curing Curing Poly- Reaction time time Silane Ex Amine acid Water Accelerator Base conditions 200° C. 250° C. [%] 10 25.5 kg 17.6 kg 32.51 20% DEA 60°/130° 140 s 35 s 0.2 DEA ADP PAA for 3 hours

TABLE 6 Delami- Delami- nation nation Re- Binder Oil strength, strength, aged maining content content Density unaged (70° C./95% RH) strength Ex [%] [%] [kg/m³] [kPa] [kPa] [%] 10 3.5 0.2 140 10.1 3.3 36

EXAMPLE 11

Resin:

116 kg DEA was transferred to a 400 l reactor and heated to 60° C. and stirred.

16.3 kg ADP was added and the mixture heated and reacted at 130° C. for 60 minutes.

Thereafter cooled to 85° C. and added (THPA) 33.8 kg. Thereafter 82.5 kg PTA was added and the temperature raised to 130° C. and kept there for 120 minutes.

Thereafter the reaction mixture was cooled to 110° C. and 100 kg water added.

The temperature stabilised at approx. 50° C. The mixture was stirred for further 15 minutes until homogenous.

The resin was cooled and transferred to a storage tank.

Resin solids content 62.2% determined at 200° C. Rest monomers 39% DEA of added, 12% THPA of added, 25% PTA of added. Average molweight about 600.

On a sample, a factory trial was carried out, whereby 4% DEA and 25% solids Acumer 1510 calculated on resin solids, 0.4% of sum solids silane and water to 25% solids content, was added and analysed.

Results of Factory Trial

Binder yield 60%

Delamination strength (EN 1607) 13.4 kPa (Terraenbatts Industri)—Aged 3.6 kPa (70° C./95% RH)

Tensile strength 5.5 kPa (Flexi A Batts)

EXAMPLE 12

Resin

24 kg DEA was transferred to a 80 l reactor and heated to 60° C. and stirred.

6.7 kg ADP was added and the mixture heated and reacted at 130° C. for 60 minutes.

Thereafter cooled to 85° C. and added 6.9 kg THPA. Thereafter 16.9 kg PTA was added and the temperature raised to 130° C. and kept there for 120 minutes.

Thereafter the reaction mixture was cooled to 110° C. and 20.5 kg water added. The temperature stabilises at approx. 50° C.

The mixture was stirred for further 15 minutes until homogenous.

The resin was cooled and transferred to a storage tank.

Resin solids content 63.4% determined at 200° C. Rest monomers 37% DEA of added, 14% THPA of added, 25% PTA of added. Average molweight about 600.

On a sample, a factory trial was carried out, whereby 4% DEA and 25% solids Acumer 1510 calculated on resin solids, 0.4% of sum solids silane and water to 25% solids content, was added and analysed.

Results of Factory Trial

Binder yield 70%

Delamination strength (EN 1607) 12.1 kPa (Terrenbatts Industri)—Aged 4.3 kPa (70° C./95% RH)

The invention is not limited to the above description, the requested rights are determined by the following claims. 

1-36. (canceled)
 37. A process for providing a binder for mineral wool products said process comprising the steps of: mixing together under reactive conditions a carboxylic acid with an alkanolamine to provide a resin, which resin is subsequently mixed with a separate carboxylic acid group containing polymer.
 38. (canceled)
 39. The process according to claim 37, wherein the carboxylic acid group containing polymer has a molecular weight lying in the ranges of 1,000-300,000.
 40. The process according to claim 37, wherein the carboxylic acid group containing polymer comprises at least one of a polyacrylic acid, polymethacrylic acid, polymaleic acid and co-polymers thereof.
 41. (canceled)
 42. The process according to claim 37, wherein the carboxylic acid is a di, tri, or tetra, carboxylic acid having a molecular weight of about 1,000 or less.
 43. The process according to claim 42, wherein the carboxylic acid is a di-carboxylic acid having the general formula: COOH—(CR₁R₂)_(n)—COOH wherein n ∃2, and wherein R₁ and R₂ are independently selected from H and a lower alkyl group.
 44. The process according to claim 42, wherein the carboxylic acid is selected from the group consisting of adipic acid, citric acid, trimellitic acid, sebacic acid, azelaic acid and succinic acid.
 45. The process according to claim 37, wherein the alkanolamine is selected from the group consisting of di- and tri-alkanolamines.
 46. The process according to claim 45, wherein the alkanolamine is a secondary beta-hydroxy alkylamine.
 47. The process according to claim 37, wherein the alkanolamine is selected from the group consisting of di-ethanolamine, 1-methyldiethanolamine, 1-ethyldiethanolamine, n-butyldiethanolamine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol and tris(hydroxymethyl)aminomethane.
 48. The process according to claim 37, wherein the mole ratio of the carboxylic acid to the alkanolamine in the binder lies in the range of 0.1-1:1-0.1.
 49. The process according to claim 37, wherein the weight percentage of the carboxylic acid group containing polymer in the binder lies in the range of 0.5-50.
 50. The process according to claim 37, wherein the alkanolamine is firstly heated to a first predetermined temperature whereafter the carboxylic acid is added and the temperature of this mixture raised to a second predetermined temperature.
 51. The process according to claim 50, wherein the first temperature is around 60° C. and wherein the second temperature is at least about 90° C.
 52. The process according to claim 37, comprising the further step of adding at least one of the following to the binder: a coupling agent, a polymerization accelerator, a curing accelerator and standard mineral wool binder additives.
 53. (canceled)
 54. The process according to claim 37, wherein a base is subsequently added to the reaction mixture.
 55. The process according to claim 54, wherein the base is selected from the group comprising NH₃, diethanolamine (DEA), triethanolamine (TEA), and any of NH₃, DEA and TEA mixed with a polyacrylic acid.
 56. The process according to claim 55, wherein weight % of base in the resin reaction mixture, calculated by weight of the solids in the reaction mixture, lies in the range of up to 20%.
 57. The process according to claim 37, wherein the weight % of the carboxylic acid group containing polymer in the mixture lies in the range up to 25%.
 58. The process according to claim 37, further comprising the step of adding a silane, in the range of 0.1%-5% by weight of the resin solids.
 59. A binder obtained by the process of claim
 37. 60. The binder of claim 59, wherein the alkanolamine comprises at least one of a dialkanolamine and a trialkanolamine, and the carboxylic acid comprises at least one of dicarboxylic acid, tricarboxylic acid and tetracarboxylic acid, said carboxylic acid having a molecular weight of about 1,000 or less. 61-63. (canceled)
 64. The binder according to claim 59, further comprising a silane.
 65. A process for providing a mineral wool product comprising the steps of contacting mineral fibres with the binder of claim 59, followed by a curing step.
 66. A mineral wool product comprising the binder of claim
 64. 67. A mineral wool product comprising the binder according to claim
 59. 68. A mineral wool product comprising the binder according to claim 59, which mineral wool product has been cured at a temperature of at least 100° C. 69-73. (canceled)
 74. The process according to claim 50, wherein: the carboxylic acid group containing polymer has a molecular weight lying in the range of 1,000-250,000; the carboxylic acid has a molecular weight of 500 or less; the weight percentage of the carboxylic acid group containing polymer in the binder lies in the range of 10-40%; the second temperature lies in the range of about 95-200° C.; a base is subsequently added to the reaction mixture in the range of up to 10% calculated by weight of solids in the reaction mixture; and further comprising the step of adding a silane in the range of 0.2-3% by weight of the resin solids.
 75. The process according to claim 50, wherein: the carboxylic acid group containing polymer has a molecular weight lying in the range of 1,000-200,000; the carboxylic acid has a molecular weight of 200 or less; the weight percentage of the carboxylic acid group containing polymer in the binder lies in the range of 15-30%; the second temperature lies in the range of about 120-150° C.; a base is subsequently added to the reaction mixture in the range of 1-5% calculated by weight of solids in the reaction mixture; and further comprising the step of adding a silane at about 1% by weight of the resin solids. 76-78. (canceled)
 79. The binder according to claim 59, having a curing time of at most about 35 seconds at 200° C.
 80. The mineral wool product according to claim 68, which mineral wool product has been cured at a temperature of at least 150° C.
 81. The mineral wool product according to claim 68, which mineral wool product has been cured at a temperature of at least 200° C. 82-85. (canceled)
 86. A method of forming a formaldehyde free co-binder solution comprising the steps of: admixing a polyacid monomer or oligomer having at least two carboxylic acids and a molecular weight of 1000 or less and a polyol having at least two hydroxyl groups with agitation for a period of time sufficient for said polyacid monomer or oligomer and said polyol to react and form a reaction product; adding a polycarboxylic acid binder to said admixture containing said reaction product; permitting said reaction product and said polycarboxylic acid binder to react and form a co-binder solution having a reduced viscosity and a reduced cure temperature.
 87. The method of claim 86, wherein said polyacid monomer or oligomer is selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, citric acid, tartaric acid, adipic acid, glutaric acid, itaconic acid, trimellitic acid, hemimellitic acid, trimesic acid, tricarballylic acid, 1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, oligomers of carboxylic acid, acrylic acid, vinyl acetate and any combination thereof.
 88. The method of claim 86, wherein said polyol is reactive with an ester group to form an ester linkage.
 89. The method of claim 86, wherein said polyol is selected from the group consisting of triethanolamine, glycerine, ethylene glycol, pentaerythritol, trimethylol propane, sorbitol, sucrose, glucose, resorcinol, catechol, pyrogallol, 1,4-cyclohexane diol, monoethanolamine and diethanolamine.
 90. The method of claim 89, wherein said polyol is selected from the group consisting of triethanolamine and glycerine.
 91. The method of claim 86, wherein said polycarboxylic acid binder has a pH of 1.5-4.5.
 92. The method of claim 86, wherein said polyacid is maleic acid, said polyol is triethanolamine, said reaction product is triethanolamine maleic acid ester, and said co-binder solution includes a maleic anhydride polyacrylic acid triethanolamine polyester co-binder.
 93. The method of claim 86, wherein said period of time is from 10 to 300 minutes.
 94. The method of claim 86, wherein said polycarboxylic acid binder is terminated by sodium hypophosphite.
 95. The method of claim 86, wherein said cure temperature is approximately 150° C.
 96. A method of forming a formaldehyde free polycarboxylic acid based co-binder solution comprising the steps of: admixing a polyacid monomer or oligomer having at least two carboxylic acids and a molecular weight of 1000 or less, a polyol having at least two hydroxyl groups, and a polycarboxylic acid binder with agitation to form an admixture; heating said admixture for a period of time sufficient to form a co-binder solution having a reduced viscosity and a reduced cure temperature of approximately 150° C.
 97. The method of claim 96, wherein said polyacid monomer or oligomer is selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, citric acid, tartaric acid, adipic acid, glutaric acid, itaconic acid, trimellitic acid, hemimellitic acid, trimesic acid, tricarballylic acid, 1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, oligomers of carboxylic acid, acrylic acid, vinyl acetate and any combination thereof.
 98. The method of claim 96, wherein said polyol is selected from the group consisting of triethanolamine, glycerine, ethylene glycol, pentaerythritol, trimethylol propane, sorbitol, sucrose, glucose, resorcinol, catechol, pyrogallol, 1,4-cyclohexane diol, monoethanolamine and diethanolamine.
 99. The method of claim 96, wherein said polycarboxylic acid binder has a pH of 1.5-4.5.
 100. The method of claim 96, wherein said polyacid is maleic acid, said polyol is triethanolamine, said reaction product is triethanolamine maleic acid ester, and said co-binder solution includes a maleic anhydride polyacrylic acid triethanolamine polyester co-binder.
 101. The method of claim 96, wherein said period of time is from 10 to 300 minutes.
 102. The method of claim 96, wherein said polycarboxylic acid binder is terminated by sodium hypophosphite.
 103. A composition for forming a formaldehyde free co-binder solution comprising: a polyacid monomer or oligomer having at least two carboxyl groups and a molecular weight of less than 1000; a polyol having at least three hydroxyl groups; and a polycarboxylic acid binder having a pH of from 1.5-4.5; wherein an active hydroxyl group to acid group molar ratio is from 0.2-1.5.
 104. The composition of claim 103, wherein said polyol is reactive with an ester group to form an ester linkage.
 105. The composition of claim 104, wherein said polyol is selected from the group consisting of triethanolamine, glycerine, ethylene glycol, pentaerythritol, trimethylol propane, sorbitol, sucrose, glucose, resorcinol, catechol, pyrogallol, 1,4-cyclohexane diol, monoethanolamine and diethanolamine.
 106. The composition of claim 103, wherein said polyacid monomer or oligomer is selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, citric acid, tartaric acid, itaconic acid, trimellitic acid, hemimellitic acid, trimesic acid, tricarballylic acid, 1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, oligomers of carboxylic acid, acrylic acid, vinyl acetate and any combination thereof.
 107. The composition of claim 103, wherein an amount of said polyacid and said polyol present in said composition is up to 90% of the total composition.
 108. The composition of claim 103, wherein said polycarboxylic acid binder is terminated by sodium hypophosphite.
 109. The composition of claim 103, further comprising an accelerator to aid in curing of said co-binder.
 110. A process for providing a binder for mineral wool products, said process comprising the steps of: mixing together under reactive conditions a di-, tri-, or tetra-carboxylic acid having a molecular weight of about 1000 or less with a di- or tri-alkanolamine to provide a resin; mixing said resin with a separate carboxylic acid group containing polymer to form a binder.
 111. The method of claim 110, wherein said di-, tri-, or tetra-carboxylic acid is selected from the group consisting of adipic acid, citric acid, trimellitic acid, sebacic acid, azelaic acid, and succinic acid.
 112. The method of claim 110, wherein said di- or tri-alkanolamine is selected from the group consisting of di-ethanolamine, 1-(m)ethyldiethanolamine, n-butyldiethanolamine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, and tris(hydroxymethyl)aminomethane.
 113. The method of claim 110, wherein said carboxylic acid group containing polymer is mixed with a base and added to the resin.
 114. The method of claim 110, wherein the reaction time is 1-3 hours.
 115. The method of claim 110, wherein said cure temperature is 150° C.
 116. A method of forming a phenol formaldehyde-free polycarboxylic acid binder solution comprising the steps of: mixing a di-, tri-, or tetra-carboxylic acid having a molecular weight of about 1000 or less, a di- or tri-alkanolamine, and a carboxylic acid group-containing polymer binder with agitation to form a mixture; heating said mixture for a period of time sufficient to form a clear, low viscous liquid having a cure temperature of 150° C.
 117. The method of claim 116, wherein said carboxylic acid is selected from the group consisting of succinic acid, citric acid, adipic acid, and trimellitic acid.
 118. The method of claim 116, wherein said alkanolamine is diethanolamine.
 119. The method of claim 116, wherein said carboxylic acid group containing polymer is mixed with a base and added to the resin.
 120. The method of claim 116, wherein said reaction time is 1-3 hours.
 121. A composition for forming a phenol formaldehyde-free binder comprising: a di-, tri-, or tetra-carboxylic acid having a molecular weight of 1000 or less; a di- or tri-alkanolamine; and a carboxylic acid group-containing binder; wherein an active hydroxyl group to acid group molar ratio is from 0.1-1.0.
 122. The composition of claim 121, wherein said alkanolamine is diethanolamine.
 123. The composition of claim 121, further comprising a curing accelerator. 